EP1385468A2 - Active ingredient combinations for hair-dyeing agents - Google Patents

Abstract

The invention relates to agents used for colouring keratin fibres, which contain, in addition to dyes and/or intermediate dye products, an active ingredient combination comprising (A) at least one silicon oil and/or one silicon gum and (B) at least one polymer, containing at least one monomer unit of formula (I), wherein n represents a whole number between 1 and 3 and Y represents a physiologically acceptable anion. The inventive agent is characterised in that it improves the hold, wet compatibility and shine of the treated fibres, especially in Asian hair.

Description

 , Nourishing active ingredient combination for hair dye "

The present invention relates to hair colorants which contain a nourishing combination of active ingredients, and to a process for coloring using this combination of active ingredients.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role.

So-called oxidation colorants are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components. Combinations of oxidation dyes and direct dyes are often used to achieve special shades. The oxidation colorants are characterized by excellent, long-lasting coloring results.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally sensitive to shampooing, so that a frequently undesirable shift in shades or even a visible "discoloration" can occur. A disadvantage of such temporary colors is that these colors add to the natural hair tone and thus only allow nuances that are darker than the original tone. Therefore, dyes based on direct dyes are often used in combination with oxidizing agent preparations to lighten the original color of the fibers in addition to the actual dyeing.

Both processes therefore require the use of strong oxidizing agents such as hydrogen peroxide solutions. This can damage the hair to be colored. This damage must then be countered with appropriate care products.

It has therefore long been customary to subject the hair to a special after-treatment. Here, usually in the form of a rinse, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the formulation, this treatment improves the combability, hold and fullness of the hair and reduces the split rate.

In addition, so-called combination preparations have recently been developed in order to reduce the complexity of the conventional multi-stage processes, in particular when used directly by the consumer.

In addition to the usual components, for example for coloring the hair, these preparations additionally contain active ingredients which were formerly reserved for the hair aftertreatment agents. The consumer thus saves one application step; At the same time, the packaging effort is reduced because one product is used less.

The active ingredients which can be used in the context of such combination preparations must meet high demands, in particular with regard to their stability, since the coloring creams usually have a high pH and the oxidizing agent preparations have a low pH. Furthermore, incompatibilities of the various active substances with one another and thus poor storage stability are to be avoided. In the context of the applications DE-A-199 14927, DE-A-199 14 926 and DE-A-44 08 506, such combinations of active substances have already been proposed for use in oxidative colorants. Nevertheless, these agents, especially on fibers that are difficult to care for, such as Japanese hair, still leave some wishes unanswered with regard to the caring properties.

There is therefore still a need for active substances or combinations of active substances with good nourishing properties and good biodegradability, in which undesired accumulations on the hair are excluded.

It has now surprisingly been found that an active ingredient combination of silicone oils and special polymers does not have the disadvantages mentioned above and at the same time improves the feel, the ability to wet comb and the gloss of the treated fibers, in particular in the case of Asian hair.

Furthermore, the compositions according to the invention are notable for their good applicability, that is to say that the compositions have a consistency which enables good adhesion to the fibers and is not too thin. It has been found that the active ingredient combination according to the invention also has a surprising synergism with regard to the thickening properties.

A first subject of the present application is therefore an agent for dyeing keratinic fibers, containing, in addition to dyes and / or dye precursors, a nourishing active ingredient combination

(A) at least one silicone oil and / or a silicone gum and

(B) at least one polymer containing at least one monomer unit of the formula (I) where n stands for an integer between 1 and 3 and Y stands for a physiologically acceptable anion.

According to the invention, keratin fibers are understood to mean furs, wool, feathers and in particular human hair.

According to the invention, physiologically compatible anions are, for example, chloride, bromide, sulfate, phosphate, acetate, propionate, citrate and lactate. The chloride is a preferred anion according to the invention.

Although it is preferred according to the invention if both components of the active ingredient combination are incorporated into the coloring cream, component (A) can also be contained in the oxidizing agent preparation in a further embodiment. In this embodiment, the agent containing the active ingredient combination according to the invention is only obtained after the two components have been mixed.

Silicones or silicone gums suitable according to the invention are in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or also anionic derivatives.

Examples of such silicones are:

Oligomeric polydimethylcyclosiloxanes (TNCI name: Cyclomethicone), in particular the tetramer and the pentamer compound, which are sold as commercial products DC 344 and DC 345 by Dow Corning, - Hexamethyl-disiloxane (INCI name: Hexamethyldisiloxane), e.g. B. the product sold under the name Abil ^® K 520,

- Polymeric polydimethylsiloxanes (INCI name: Dimethicone), e.g. B. the products sold under the name DC 200 by Dow Corning,

- Polyphenylmethylsiloxane (INCI name: Phenyl Trimethicone), e.g. B. the commercial product DC 556 Fluid from Dow Corning,

- Silicon-glycol copolymers (INCI name: Dimethicone Copolyol), e.g. B. the commercial products DC 190 and DC 193 from Dow Corning,

- esters and partial esters of silicone glycol copolymers, such as, for example, by the company Fanning under the trade name LIM Fancorsil ^® (INCI name: dimethicone copolyol Meadowfoamate) are distributed,

- Dimethylsiloxanes with hydroxy end groups (INCI name: Dimethiconol), e.g. B. the commercial products DC 1401 and Q2-1403 from Dow Corning,

- amino-functional polydimethylsiloxanes and hydroxylamino-modified silicones (INCI name: inter alia amodimethicone and quaternium-80), such as the commercial products XF42-B1989 (manufacturer GE Toshiba Silicones) Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning ^® 939 (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt ), anionic silicone oils, such as the product Dow Corning ^® 1784.

According to a preferred embodiment, the preparations according to the invention contain a combination of a volatile and a non-volatile silicone. Volatile for the purposes of the invention are those silicones which have a volatility which is equal to or greater than the volatility of the cyclic, pentameric dimethylsiloxane. Such combinations are also available as commercial products (eg Dow ^Corning® 1401, Dow ^Corning® 1403 and Dow ^Corning® 1501, in each case mixtures of a cyclomethicone and a dimethiconol). According to a particularly preferred embodiment, a dialkylpolysiloxane or one of its derivatives is used as component (A). The alkyl groups are preferably methyl, ethyl, i-propyl and n-propyl. Dimethylpolysiloxane or one of its derivatives is particularly preferably used. Preferred are the derivatives of dialkylpolysiloxanes that are arrio-functional, the ammofunctional derivatives of dimethylpolysiloxane are particularly preferred. A very particularly preferred derivative is commercially available under the INCI name Amodimethicone.

The preparations according to the invention preferably contain the silicones in amounts of 0.05-10% by weight, in particular 0.1-5% by weight, based on the entire application preparation.

In a first preferred embodiment, the components (B) of the nourishing active ingredient combination according to the invention are cationic polymers. These are in particular the homopolymers of the dimethyldiallylammonium salts (corresponding to the monomer units of the formula (I)) and the copolymers of the dimethyldiallylammonium salts with esters and amides of acrylic acid and / or methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimemyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.

In a second preferred embodiment, the components (B) of the nourishing active ingredient combination according to the invention are amphoteric polymers. These are in particular the copolymers of the dimethyldiallylammonium salts (corresponding to the monomer units of the formula (I)) with acrylic acid and / or methacrylic acid. The copolymers with acrylic acid are particularly preferred. The quat under the trade name Mer- ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer, INCI name: Polyquaternium-22) marketed product is an example of such polymers.

Furthermore, those amphoteric copolymers are particularly preferred which, in addition to the monomer units of the formula (I) and the acrylic acid and / or methacrylic acid units, still contain at least one nonionic comonomer. Examples of such nonionic comonomers are the esters or amides of acrylic acid and / or methacrylic acid. The ^® under the trade name Merquat Plus 3330 (Dimethyldiallylammo- niumchlorid-acrylic acid-acrylamide terpolymer, INCI name: Polyquaternium-39) marketed product is an example of such a preferred polymer.

In a first preferred embodiment, the colorants according to the invention contain at least one dye precursor. With regard to the dye precursors used in the colorants according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as dye precursors

• developer or coupler type oxidation dye precursors, and

• contain precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

The colorants according to the invention preferably contain at least one developer component as the dye precursor. Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used.

It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which G ¹ represents a hydrogen atom, a Ci to C alkyl radical, a - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (d- to C ₄ ) - alkoxy- (Cι- to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C 1 -C 12 -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a Ci to C ₄ alkyl radical, a CJ to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (Ci-C) - alkoxy- (Cι- to C ₄ ) alkyl radical or a Ci to C alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a Ci to C alkyl radical, a d to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Ci to C -Hydroxyalkoxyrest, a CJ to C ₄ -Acetylaminoalkoxyrest, a Ci to C - Mesylaminoalkoxyrest or a Ci to C ₄ -Carbamoylaminoalkoxyrest;

G ⁴ represents a hydrogen atom, a halogen atom or a C 1 -C ₄ -alkyl radical or if G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Ci to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C 1 -C ₄ -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms according to the invention are F, CI or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, the amino groups, C 1 -C ₄ -monoalkylamino groups, C ₄ -C ₄ - Dialkylamino groups, - to C4-trialkylammonium groups, Ci- to C ₄ - monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-CMor-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylene diamine, 2,5-dimethyl-p-phenylene diamine, N, N-dimethyl-p-phenylene diamine, N, N-diethyl-p-phenylene diamine, N, N-dipropyl-p -phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (ß-hydroxyemyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) -amino-2-methyl-aniline, 4-N, N-bis-hydroxyemyl) -amino-2-chloroariline, 2- (ß-hydroxyethyl) -p-phenylene diamine, 2-fluoro-p-phenylene diamine, 2nd -Isopropyl-p-phenylenediamine, N- (ß-

Hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phe-nylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- ( ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß-

Acetylaminoethyloxy) -p-phenylenediamine, N- (ß-Memoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyemyl) -p-phenylenediamine.

It can further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted with amino and / or hydroxyl groups.

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts: in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C 1 -C ₄ -alkyl radical, by a C 1 -C ₄ -hydroxyalkyl radical and / or by a bridging Y or the is optionally part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring which is composed of one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or Ci to Cβ alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently represent a hydrogen or halogen atom, a Cj to C ₄ alkyl radical, a d to C monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Ci to C ₄ aminoalkyl radical or a direct connection to bridge Y,

1 8 Q in I I 1 * 7

G, G, G, G, G and G independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C 1 -C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) only have one bridge Y contain per molecule and - the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (E2) are defined analogously to the above statements. Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol , N, N'- bis (ß-hydroxyethyl) -N, N ^, -bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) -te-tramethylenediamine, N, N '-Bis- (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -tetramethylenediamine, N, N'-bis- (4-memyl-aminophenyl) -tetramethylenediamine, N, N'-diethyl -N, N'-bis- (4 ^, -amino-3 ^l -methylphenyl) -ethylenediamine, bis- (2-hydroxy-5-aminophenyl) -methane, N, N'-bis- (4'-aminophenyl) - 1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) p-phenylenediamine and l, 10-bis (2 ', 5'-diaminophenyl) -l, 4,7,10-tetraoxadecane and their physiologically tolerable salts.

Very particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis (ß-hydroxyemyl) -N, N'-bis- (4 ^, -aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hy-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -l, 4-diazacycloheptane and l, 10-bis (2 ', 5'-diaminophenyl ) -l, 4,7,10-tetraoxadecane or one of its physiologically tolerable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a Cp to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ to C4 polyhydroxyalkyl radical, one

Alkyl (Ci to C ₄₎ alkoxy (Cr to _C4), a Ci to C ₄ aminoalkyl radical, a

Hydroxy- (Cι to C ₄ ) alkylamino, a Ci to C -hydroxyalkoxy, a Ci to C -Hy-droxyalkyl- (Cι-to C) -aminoalkylrest or a (Di-Ci- to C ₄ -alkylamino) - (d- to C ₄ ) -alkylrest, and

G ¹⁴ represents a hydrogen or halogen atom, a d- to C ₄ -alkyl radical, a Ci- to C ₄ -monohydroxyalkyl radical, a C ₂ - to C -polyhydroxyalkyl radical, a (Ci- to C ₄ ) -alkoxy- (Cι - to C ₄ ) alkyl, a Ci to C4 aminoalkyl or a Ci to C ₄ cyanoalkyl,

G ¹⁵ represents hydrogen, ad- to C ₄ -alkyl, ad- to C ₄ -mono-hydroxyalkyl, C ₂ - to C ₄ -polyhydroxyalkyl, phenyl or benzyl, and

G ' ⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4- aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl- phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2, 6-dichlorophenol, 4-arnino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2- (diethylaminomethyl) phenol.

Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol. Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.

Preferred pyridine derivatives are in particular the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) -amino-3-aminopyridine , 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimemyl-ammo-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2.5, 6-tri-aminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE-A-38 43 892, DE-A-41 33 957 and patent applications WO-A-94/08 969, WO-A-94/08 970, EP- A-740 931 and DE-A-195 43 988 can be described, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-l- (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4, 5-di-amino-1 - (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-amino-1, 3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1 - methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-l-ethyl-3 -methylpyrazole, 4,5-diamino-l-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5- (ß-amino ethyl) - amino-1, 3-dimethyl-pyrazole, 3, 4,5-triaminopyrazole, 1-methyl-3, 4,5-triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3.5 -Diamino-4- (ß-hydroxyethyl) - amino-1 -methylpyrazole. Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided that there is a tautomeric equilibrium:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a d- to C ₄ -alkyl radical, an aryl radical, a Ci to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical a (d- to C ₄ ) -alkoxy- (Cι- to C ₄ ) -alkyl radical, a Ci- to C -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Ci to C ₄ ) -alkylamino- (Cι- to C ₄ ) -alkyl radical, a di- [(Ci- to C) -alkyl] - (d- to C) -aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or one Form a heterocycle with 5 or 6 chain links, a Ci- to C ₄ -hydroxyalkyl or a di- (Cι- to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) - aminoalkyl radical, the X radicals are independent from each other for a hydrogen atom, ad- to C ₄ -alkyl residue, an aryl residue, a C _\ - to C ₄ -hydroxyalkyl residue, a C ₂ - to C ₄ -polyhydroxyalkyl residue, a Ci- to C ₄ -aminoalkyl residue, a ( Ci to C ₄ ) alkyl amino- (Ci- to C ₄ ) -alkyl radical, a di - [(Cι- to C ₄ ) alkyl] - (Ci- to C ₄ ) -aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or a heterocycle with 5 or Form 6 chain links, a d- to C ₄ -hydroxyalkyl- or a di- (Cι- to C - hy-hydroxyalkyl) -aminoalkyl radical, an amino radical, a Ci- to C ₄ -alkyl or di- (Cι- to C _4- hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0 if p + q is equal to 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

According to the invention, the substituents used in formula (E4) are defined analogously to the above statements.

If the pyrazole- [1,5-a] pyrimidine of the above formula (E4) contains a hydroxyl group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

Among the pyrazole [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

Pyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl-pyrazole- [1,5-a] -pyrirmdm-3,7-diamine;

Pyrazole- [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazole- [1,5-a] pyrimidin-7-ol;

3-aminopyrazole- [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazole- [1,5-a] pyrimidm-7-ylamino) ethanol;

2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;

2- [(3 - aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

2 - [(7-aminopyrazole [l, 5-a] -pyrimidm-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

5, 6-dimethylpyrazole- [1, 5-a] pyrimidine-3, 7-diamine; 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazole- [1,5-a] pyrimidine; as well as their physiologically tolerable salts and their tautomeric forms if there is a tauomeric equilibrium.

The pyrazole [1,5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

The agents according to the invention can furthermore contain cationic dye precursors of the coupler and / or developer type, as described, for example, in the published documents WO-Al-99/03 819, WO-A2-99 / 03 834, WO-Al-99/03 836 , WO-Al-99/48 856, WO-Al-99/48 874, WO-Al-99/48 875, WO-A2-00 / 42 971, WO-Al-00/42 979, WO-Al- 00/42 980, WO-Al-00/43 356, WO-Al-00/43 367, WO-Al-00/43 368, WO-Al-00/43 386, WO-Al-00/43 388, WO-Al-00/43 389, WO-Al-00/43 396, EP-A1-0 984 006, EP-Al-0 984 007 and EP-A1-0 989 128 can be described.

Particularly preferred cationic dye precursors are

[2- (2 ^ 5-diamino-phenoxy) -emyl] -diemyl-memyl-ammonium chloride,

[2- (4'-Ammo-phenylamino) propyl] trimethylammonium chloride,

[4- (4 ^, -amino-phenylamino) -pentyl] -diemyl- (2-hydroxyemyl) -ammonium chloride,

1 - {[5'- amino-2 ^, - (2 "-hydroxyethylamino) -phenylcarbamoyl] -methyl} - 1, 4-dimethyl-piperazin-1 -ium chloride, 1,4-bis-l- {3- [3 '- (2 ^l 5 "-diammophenoxy) propyl] -3H-imidazole-l-ium} -butane dichloride, 1,3-bis- [3' - (2", 5 ^, '-diamino phenoxy) -propyl] -3H-imidazol-l-ium chloride

N, N ^, -Bis- [3-N-methyl-4-N- (4'-amino-aniline) -ethyl] - 1, 1, 4,4-tetramethyl-diammonium-1,3-propane-dibromide,

1, 3-bis- 1 - {3- {3 '- [(4 "-amino-3" -methyl-aniline) -N-propyl]} -3H-imidazole-1 -ium} -propane dichloride l, 3-bis-l- {3- {3 '- [(4 "amino-aniline) -N-propyl]} - 3H-imidazole-l -ium} -propane dichloride

1,3-bis-1 - {3- {3 '- [(4 "-amino-2" -methylaniline) -N-propyl]} -3H-imidazole-1 -ium} -propane dichloride 3- [3- (4'-Ammo-phenylamino) propyl] -l-methyl-3H-imidazole-1 -ium chloride

[3- (2 \ 5'-Diamino-phenoxy) propyl] -3-methyl-3H-imidazole-1 -ium chloride

3- [3- (4'-Al-mo-3 ^, -memyl-phenylamino) -propyl] -l-methyl-3H-imidazole-1-ium chloride

3- [3- (4'-ammo-2'-memyl-phenylamino) -propyl] -l-methyl-3H-imidazol-l-ium chloride

1 - [2- (4'-Ammo-2'-memoxyphenylarnino) ethyl] -3-methyl-3H-imidazole-1-chloride

3- [3- (4'-Ammo-2 ^, -fluorophenylarnino) propyl] -l-methyl-3H-imidazole-1-ium chloride

3- [3- (4'-amino-2'-cyano-phenylamino) -propyl] -l-methyl-3H-imidazol-l-ium chloride

3- [2- (2 ^ 5'-Diamino-phenyl) -ethyl] -l-methyl-3H-imidazole-1 -ium chloride l- {2 - [(4'-ammo-phenyl) -emyl-aπüno ] -ethyl} -3-methyl-3H-imidazol-l-ium chloride

N, N-Bis- [2- (3 ^, -methyl-3H-imidazole-1 -ium) -emyl] -4-amino-aniline chloride

3- [2- (4'-amino-phenylamino) -butyl] -l-memyl-3H-imidazol-l-ium chloride

[2- (2 ^ 4'-Diammo-phenoxy) -emyl] -diemyl-memyl-ammonium-chloride l- [3- (2 \ 4'-Diammo-phenoxy) -propyl] -3-memyl-3H-imidazole -l-ium-chloride l- ^ S'-hydroxy ^ '- methyl-phenylcarbamoy -methylJ-S-methyl-SH-imidazole-l-ium-chloride l, 4-bis-l- {3- [3- ( 2 4'-diamino-phenoxy) -propyl] -3H-imidazole-1-ium} -butane dichloride

3 - [(3'-Hydroxy-4 ^, -methanesulfonylamino-phenylcarbamoyl) methyl] -l-methyl-3H-imidazole-1-chloride

3 - ^{[(3, 5'-Dichloro-2-hydroxy-4-methyl-phenylcarbamoyl)} -methyl] -l-methyl-3H-imidazol-1 -ium-chloride

1 - ^{[(3, 5'-Dichloro-2-hydroxy-4-methyl-l)} methyl] - 1, 4-dimethyl- piperazin-1 -ium-chloride

3 - [(4'-Acetylamino-2 ^, -hydroxyphenylcarbamoyl) methyl] -l-methyl-3H-imidazole-l-ium chloride

4- {3 - [(3'-Hydroxy-naphthalene-2 ^, carbonyl) amino] propyl} -4-methylmorpholin-4-ium iodide

3 - [(-Hydroxy-naphmalen-2 ^, -ylcarbamoyl) -memyl] -l-memyl-3H-imidazole-l-ium chloride

3 - [(5'-Acetylamino-r-hydroxy-naphthalene-2 ^l -ylcarbamoyl) methyl] -l-methyl-3H-imidazole-1 -ium chloride

3 - [(1'-Hydroxy-S'-memanesulfonylamino-naphthalene ^ '- ylcarbamoy ^ -methyl] - 1 -methyl-

3 H-imidazole-1 -ium chloride [3- (4'-Arnmo-2 ^ 5'-dimemyl-2H-pyrazol-3'-ylamino) propyl] - (2-hydroxyethyl) -dimethylammonium chloride l ^ -Bis - ^ '- hydroxy ^ '-memyl-phenylcarbamoy -memylJ-SH-imidazole-l-ium chloride l- [2- (6'-amino-benzo [1,3, dioxol-5'-ylamino) -ethyl] -3-methyl-3H -imidazole-l-ium chloride

3- [2- (6 * -Ammo-benzo [1,3] dioxol-5'-ylammo) -emyl] -l- (4- {3- [2- (6 ^,, -amino-benzo [l, 3] dioxol-5 ^{, l} -ylamino) -emyl] -3H-imidazole-l-ium} -butyl) -3H-imidazole-l-ium-dichloride

3- [3- (3'-Amino-5 ^, -methylpyrazolo [1,5-a] pyrimidm-7'-ylamino) propyl] -1 - (2-hydroxyethyl) -3H-imidazole-1 -ium -chloride

1,3-bis-1 - {3- {3 - [(2'-amino-aniline) -N-propyl]} -3H-imidazole-1 -ium} -propane-dibromide

N, N ^, -Bis- [3-N- (2'-amino-anilm) -N-propyl] -l, 1,3,3-tetramemyldiammorιium-1,3-propanedibromide

3- [3- (2 ^, -aminophenylamino) propyl] 1-methyl-3H-imidazole-1-ium chloride

[2- (2'-Ammophenylarnmo) -emyl3-trimemylammonium chloride and

3 - (4'-Hydroxy-1'-methyl 1- 1 H-indol-5'-ylmethyl) - 1-methyl-pyridinium methosulfate.

Furthermore, colorants are preferred according to the invention which contain at least one coupler component as a dye precursor. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Suitable coupling substances are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl-3 - methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1, 3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6 -methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components preferred according to the invention are:

m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy -4-aminophenoxyethanol, "2,6-dimethyl-3 - aminophenol, 3- Trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3 - (Diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihy- droxy-5- (methylamino) benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxy ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4- diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -l-methylbenzene and l-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and their derivatives such as 3, 4-diaminobenzoic acid and 2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinomino methyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-

Chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 -dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-

Diamino-2,6-dimethoxy,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy naphthalene, 1.7 -Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxy-naphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives, such as, for example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamine-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine,

2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-

Dihydroxy-2-methylpyrimidine, or - Methylenedioxybenzene derivatives such as l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxy naphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

If the dye precursors are arnino compounds, the known acid addition salts can be prepared from them in the usual way. All statements in this document and accordingly the claimed scope of protection therefore relate both to the compounds present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

The oxidation dye precursors of the developer / coupler type are contained in the agents according to the invention preferably in amounts of 0.01 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total agent.

According to the invention, precursors of nature-analogous dyes are also preferred as dye precursors. Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of an etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Derivatives of 5,6-dihydroxyindoline of the formula (Ia) are particularly suitable as precursors of naturally analogous hair dyes, in the independently of each other

- R ¹ represents hydrogen, a _Cι-C4 alkyl group, a Cι-C hydroxyalkyl group, or a C ₂ -C ₄ polyhydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a Ci-d-alkyl group,

- R ⁴ represents hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ represents a C 1 -C ₄ -alkyl group, and

- R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially that 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (Ib) are also outstandingly suitable as precursors of nature-analogous hair dyes,

in the independently of each other

- R ¹ represents hydrogen, a dC ₄ -, a C ₁ -C -hydroxyalkyl group or a C ₂ -C - polyhydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

- R ³ represents hydrogen or a C 1 -C ₄ alkyl group,

- R ⁴ stands for hydrogen, a Ci-d-alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a -C-C ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ ,

- And physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, particular mention should be made of N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochloride, sulfates and hydrobromides can be used. The indole or indoline Derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In a further embodiment it can be preferred according to the invention to use the indoline or indole derivative in hair colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, ornitbin, lysine, serine and histidine, in particular arginine.

In a second preferred embodiment of the present invention, the colorants contain at least one substantive dye. It does not matter for the teaching essential to the invention whether the colorant is based only on substantive dyes or whether it contains these in order to achieve the desired coloring effects in combination with the above-mentioned dye precursors.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyemyl) - aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1 - (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, l-amino-4- (2 ^l -hydroxyethyl) amino -5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, l- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-l, 4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid and its salts, 2-amino-6-chloro-4-nitrophen ol, 4-emylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

The agents according to the invention can also contain a cationic direct dye. Are particularly preferred (i) Cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic

Blue 26, Basic Violet 2 and Basic Violet 14, (ii) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and (iii ) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11.

Preferred cationic direct dyes of group (iii) are in particular the following compounds:

CH ₃ SO ₄ ^"

CI ^"

The compounds of the formulas (DZl), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of group (iii).

The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

The preparations according to the invention can furthermore also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, sedre and alkanna root ,

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, the hair colorants according to the invention, due to the manufacturing process for the individual dyes, may contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in disk form from the Federal Association of German Industry and Commerce for Medicines, Reformed Products and Personal Care Products, Mannheim.

Hair dyes, especially if the coloring is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually weakly acidic to alkaline, i.e. H. adjusted to pH values in the range from about 5 to 11. For this purpose, the colorants contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2 - methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides. Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are particularly preferred in this group. It is also possible to use ω-amino acids such as ω-aminocaproic acid as an alkalizing agent. Ammonia is a very particularly preferred alkalizing agent.

If the actual hair colors are formed as part of an oxidative process, customary oxidizing agents such as, in particular, hydrogen peroxide or its adducts with urea, melamine or sodium borate can be used. However, oxidation with atmospheric oxygen as the only oxidizing agent can be preferred. It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for enhancing the action of a small amount of oxidizing agents present. The enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases. In particular in the case of hair that is difficult to dye, the preparation with the dye precursors can be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, rinsing is then carried out and, if desired, re-shampooing. In this embodiment, according to a first variant, in which the previous application of the dye precursors is said to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxydisulfate solutions as the oxidizing agent can be preferred.

Regardless of which of the above-mentioned procedures is chosen in the context of the method according to the invention, the formation of the color can be supported and increased by adding certain metal ions to the agent. Such metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

Regardless of the type of colorant, it is preferred according to the invention to mix the colorant with an oxidizing agent preparation immediately before use.

A second subject of the present invention is therefore a process for dyeing keratin fibers in which one of the agents according to the invention is mixed with an oxidizing agent preparation immediately before use, the resulting application application preparation is applied to the fibers and rinsed off after a contact time.

In a further embodiment of the present invention, first pure coloring cream is applied to the hair and, after an exposure time, an agent which can be obtained by mixing the actual coloring cream with the oxidizing agent preparation.

A third object of the present invention is therefore a process for dyeing keratin fibers, in which one of the agents according to the invention is applied to the fibers, after a contact time a second preparation which is obtained immediately before use by mixing one of the agents according to the invention with an oxidizing agent preparation , is applied to the fibers and the fibers are rinsed thoroughly after an exposure time.

Although in principle all oxidizing agents known in hair coloring can be used, hydrogen peroxide is preferred according to the invention. The oxidizing agent preparation based on the hydrogen peroxide preferably has a pH of 1 to 6, in particular 2 to 4. Immediately before use, the dye (product) preparation and the oxidizing agent preparation are usually mixed in a ratio of 4: 1 to 1: 3, in particular 2: 1 to 1: 1. The resulting application preparation should preferably have a pH in the range from 6 to 12, in particular from 9 to 11. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can be in a range between 10 and 60 ° C, in particular between 15 and 40 ° C. It is preferably used at the temperature of the scalp. To shorten the exposure time or to improve the coloring result, application can be carried out with the addition of heat, for example under a heat hood. After an exposure time of about 5 to 60, in particular 15 to 30, minutes, the hair dye is rinsed off the hair to be dyed. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a coloring shampoo was used. In a preferred embodiment of the invention, the use preparation contains at least one further quaternary ammonium compound. According to the invention, this quaternary ammonium compound can be part of the coloring cream and / or the oxidizing agent preparation. However, it is preferred according to the invention that the further quaternary ammonium compound is part of the oxidizing agent preparation.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimemylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the quaternium-27 and quaternium-27 compounds known under the INCI names. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Stearyltrimethylammonium chloride is particularly preferred.

Other preferred quaternary ammonium compounds are also the so-called ester quats. These compounds are known substances which contain both at least one ester function and at least one quaternary arrimonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

Further preferred quaternary ammonium compounds according to the invention are the alkylamidoamines. The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound from this group of substances which is particularly suitable according to the invention represents the stearamido propyl dimethylamine commercially available under the name Tegoamid ^® S 18.

A fourth object of the present invention is a two-component kit for dyeing keratin fibers, comprising a first preparation according to one of claims 1 to 18 and a second preparation containing at least one oxidizing agent and at least one further quaternary ammonium compound.

With regard to the oxidizing agents and other quaternary ammonium compounds which can be used in the context of this subject, reference is made to the above statements.

The agents according to the invention can furthermore contain all active substances, additives and auxiliary substances known for such preparations. In many cases, these agents contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear one

Alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acyl sarcosides with 10 to 18 carbon atoms in the acyl group, Acyl taurides with 10 to 18 carbon atoms in the acyl group, acyl isethionates with 10 to 18 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha Olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated Cg-C ₂₂ carboxylic acids, such as oleic acid, stearic acid, Isostearic acid and palmitic acid.

Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, Ci2-C ₂ 2 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C8-C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R * O- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

And Cio-alkyl groups essentially of Cι ₂ - - and Cι alkyl groups essentially of C ₈ - to Ci6 alkyl groups or consists essentially of C ₁₂ - to those alkyl polyglycosides in which R ¹ consists essentially of C ₈ are particularly preferred Ci6 alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose se and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(_) - or -SOs ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylarninoethyl-hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cg-Cis-alkyl or acyl group, have at least one free amino group in the molecule. contain group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkylaminopropionate, the cocoacylarrύnoemylaminopropionate and the C ₁₂ - ₁ 8-acylsarcosine.

In addition to the quaternary ammonium compounds already mentioned above, the quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that mixtures of substances with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when converting fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. be applied. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the agents according to the invention can preferably also contain a further conditioning active ingredient selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that have a quaternary nitrogen atom, for example in the form of a

Ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimemylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and sold under the names Polyquaternium-2, Polyquaternium-17, Polyquaternium-18 and

Polyquaternium-27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred. Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline, and the substances known under the INCI names linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate and Stearamidopropyl PG-Dimonium Chloride Phosphate. These are sold, for example, by Mona under the trade names Phospholipid EFA ^® , Phospholipid PTC ^® and Phospholipid SV ^® .

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride and acrylate copolymers Octylacrylamide / methyl methacrylate / tert-butylaminoemyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl / vinyl acetate / butyl maleate / copolymers / Maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide particles,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, structurants such as maleic acid and lactic acid,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, Perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances which improve the fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl l-alkylamidoethyl -2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those from groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts from green tea, oak bark, nettle, hamamelis, hops, chamomile, burdock root, horsetail, white dome, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat , Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root ,. Cholesterol,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

Antioxidants.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The following examples are intended to explain the subject matter of the present application in more detail.

Examples

Unless otherwise stated, the following information is in percent by weight.

The following coloring creams 1 to 8 were produced: Example 1:

Cetylstearyl alcohol sulfate sodium salt (INCI name: Sodium Cetearyl Sulfate) (Cognis)

Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

2-octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis) ethylene glycol distearate (INCI name: Glycol Distearate) (Cognis) vegetable-based glycerol mono-distearate-potassium stearate mixture (INCI name: Glyceryl Stearate SE) (Cognison) aminofunctional INCI name: Amodimethicone) (GE-Toshiba - Silicones)

Dimemyldiallylammonium chloride-acrylic acid-acrylamide teφolymer (approx.9.5% active substance content; INCI name: Polyquaternium-39) (Nalco) fumed silica (INCI name: silica) (Degussa)

Examples 2 to 4:

2-Amino-2-methylpropanol (TNCI name: Aminomethyl Propanol) (CSC Chemie) Example 5:

Examples 6 to 8

Example 9:

¹⁰ Ci _ö -is fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis)

¹¹ l-hydroxyethane-l, l-diphosphonic acid (approx. 60% active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Cognis)

Immediately before use, the coloring creams of Examples 1 to 3 and 5 to 8 were each mixed with the oxidizing agent preparation according to Example 9 in a ratio of 1: 1. In the case of Example 4, a mixing ratio of coloring cream to oxidizing agent preparation according to Example 9 was set at 1: 2. The resulting application preparations were each applied to a light brown, 50% gray strand of normal hair. After a contact time of 30 minutes at 25 ° C., the tress was rinsed out with water, shampooed and dried with a hair dryer.

The colorations obtained are summarized in Table I. All strands were characterized by their good wet and dry combability, were easy to unravel and had a pleasant volume and a lot of "shine. Table I:

Table II: Color mixtures Fl to F7;

The amounts in Table II are% by weight and relate to the mass of the coloring creams from the corresponding Examples 10 to 16.

Formulation examples 17 to 19:

Table III: Color mixtures F8 to FlO

The amounts in Table III are% by weight and relate to the mass of the coloring creams from the corresponding Examples 17 to 19.

Claims

claims

1. Agent for dyeing keratin fibers, containing in addition to dyes and / or Farbstoffvoφrodukte a nourishing active ingredient combination

(A) at least one silicone oil and / or a silicone gum and

(B) at least one polymer containing at least one monomer unit of the formula (I)

where n stands for an integer between 1 and 3 and Y stands for a physiologically acceptable anion.

2. Composition according spoke 1, characterized in that a dialkylpolysiloxane or one of its derivatives is used as component (A).

3. Composition according to claim 2, characterized in that a dimethylpolysiloxane or one of its derivatives is used as component (A).

4. Agent according to one of claims 2 or 3, characterized in that component (A) is an amino-functional derivative of dialkylpolysiloxane.

5. Composition according to claim 4, characterized in that component (A) is amodimethicone.

6. Composition according to one of claims 1 to 5, characterized in that component (B) is a cationic polymer.

7. Composition according spoke 6, characterized in that component (B) is a homopolymer of monomer units of the formula (I).

8. Composition according spoke 6, characterized in that component (B) is a copolymer of the monomer unit of formula (I) and esters or amides of acrylic acid and / or methacrylic acid.

9. Composition according spoke 8, characterized in that component (B) is a copolymer of the monomer unit of formula (I) and acrylamide.

10. Composition according to one of claims 1 to 5, characterized in that component (B) is an amphoteric polymer.

11. Composition according spoke 10, characterized in that component (B) is a copolymer of the monomer unit of formula (I) and acrylic acid and / or methacrylic acid.

12. Composition according spoke 11, characterized in that component (B) is a copolymer of the monomer unit of formula (I) and acrylic acid.

13. Composition according to one of claims 10 to 12, characterized in that component (B) contains at least one monomer unit selected from esters or amides of acrylic acid and / or methacrylic acid.

14. Composition according spoke 13, characterized in that component (B) is a copolymer of the monomer unit of formula (I), acrylic acid and acrylamide.

15. Composition according to one of claims 1 to 14, characterized in that it contains at least one developer component as Farbstoffvoφrodukt.

16. Composition according to one of claims 1 to 15, characterized in that it contains at least one indole and / or indoline derivative as Farbstoffvoφrodukt.

17. Composition according to one of claims 1 to 16, characterized ^{* in} that it contains at least one coupler component.

18. Agent according to one of claims 1 to 17, characterized in that it contains at least one substantive dye.

19. A process for dyeing keratin fibers, characterized in that one of the agents of claims 1 to 18 is mixed with an oxidizing agent preparation immediately before use, the resulting application preparation is applied to the fibers and rinsed off again after an exposure time.

20. A process for dyeing keratin fibers, characterized in that one of the agents of claims 1 to 18 is applied to the fibers, after an exposure time, a second preparation which is mixed with one of the agents of claims 1 to 18 immediately before use Oxidizing agent preparation is obtained, is applied to the fibers and the fibers are rinsed thoroughly after an exposure time.

21. The method according to any one of claims 19 or 20, characterized in that the application preparation contains at least one further quaternary ammonium compound.

22. The method according spoke 21, characterized in that the further quaternary ammonium compound is contained in the oxidizing agent preparation.

23. 2-component kit for dyeing keratin fibers, comprising a first preparation according to one of claims 1 to 18 and a second preparation containing at least one oxidizing agent and at least one further quaternary ammonium compound.